Pyrolytic process and apparatus for producing enhanced amounts of aromatic compounds

ABSTRACT

Various embodiments of a process for pyrolyzing hydrocarbonaceous material are provided. In one embodiment the process for pyrolyzing hydrocarbonaceous material includes charging a reactor with a feed material comprising hydrocarbonaceous material, heating the feed material, and collecting liquid product from the reactor which is anaerobic in operation. At least 5% of the organic carbon atoms which are not present in an aromatic ring of a compound of the feed material are present in an aromatic ring of a compound in a liquid portion of the product.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a Continuation of U.S. patent applicationSer. No. 11/664,647, entitled “Pyrolytic Process and Apparatus ForProducing Enhanced Amounts of Aromatic Compounds” filed Sep. 11, 2007,which is a U.S. National Stage Application of PCT/US04/33796 entitled“Pyrolytic Process and Apparatus For Producing Enhanced Amounts ofAromatic Compounds” filed Oct. 13, 2004.

BACKGROUND

Pyrolytic processes are known in which waste polymer present in scrap,for example, thermoplastic components, tires, etc., are heated toproduce products such as liquid oils, gases, and carbon black. However,there is difficultly in achieving commercial viability for suchprocesses when the yield in recovering aromatic hydrocarbons is low, forexample, such that the cost of recovering products is more costly thanthe cost associated with deriving these materials directly frompetroleum.

U.K. Patent No. 1,481,352 discloses a method of thermal decomposition ofhydrocarbons by at least partially indirectly contacting thehydrocarbons with a hot gas. The gas is let off after heat exchangeseparately from the gaseous products formed in the decomposition. Tiresare heated in a tube by hot gases flowing through the jacket around thetube. In another embodiment the tube has a grid region to which acombustion gas is fed to aid carbonization by direct gas heating at thegrid carbon interface. Steam or CO₂ may be fed to the grid to form watergas or reduce gas to aid combustion.

U.S. Bureau of Mines report of investigation #7302 discloses a method ofdestructive distillation of scrap tires. A report was made of testsconducted under a variety of conditions. Solid, liquid, and gaseous wereproduced, recovered and analyzed. The quantities of various productswere shown to be dependent on test temperature variability incomposition of the liquid and gaseous products which changes intemperature was also reported.

U.S. Pat. No. 4,746,406 to Timmann discloses a process for the pyrolyticreprocessing of plastic, rubber, or other hydrocarbon materials in whichthe resultant pyrolysis gas is brought in a cooling stage to atemperature just above the freezing point of water and to a pressure ofapproximately 0.8 to 1.4 bar of overpressure. The resultant condensateis then separated and heated to a normal storage temperature and thesuper atmospheric pressure on the condensate reduced to atmosphericpressure. The gas produced thereby comprising C1 to C4 hydrocarboncompounds is supplied to the pyrolysis process as special product gas. Asubstantial increase in the proportion of aromatic compounds in thepyrolysis gas is reported.

Although the pyrolytic processes of the prior art can generate reusableproducts, the resulting yield of useful products can render the processeconomically unfeasible. The cost of these processes is increased evenfurther when the feed material must be sorted based upon its materialcomposition.

SUMMARY

The example embodiments of the present invention provide for processesfor pyrolyzing hydrocarbonaceous material to yield liquid productcontaining an enhanced amount of aromatic compounds. In one embodimentthe process for pyrolzing hydrocarbonaceous material includes charging areactor with feed material comprising hydrocarbonaceous material,heating the feed material, collecting product from the reactor which isanaerobic in operation. At least 5% of the organic carbon atoms whichare not present in an aromatic ring of a compound of the feed materialare present in an aromatic ring of a compound in a liquid portion of theproduct.

In another embodiment a process for pyrolyzing hydrocarbonaceousmaterial includes charging a reactor having a volume of at least 1.7cubic meters with feed material that comprises carbonaceous material,heating the feed material at an initial heat flux rate that ranges fromabout 7×10⁻⁴ kW·m²/kg² to about 3.0 kW·m²/kg² and collecting liquidproduct from the reactor which is anaerobic in operation.

An embodiment of the invention also provides for a reactor apparatus forthe pyrolysis of hydrocarbonaceous material, the reactor apparatusincludes an upper stage comprising an inclined upper inner wall vesselhaving an upper material input port and a lower material output, anupper outer wall vessel having an upper gas output port and lower gasinput port and surrounding the inner wall vessel such that a gasconveying space is interposed between the inner wall vessel and theouter wall vessel; a lower stage comprising an inclined lower inner wallvessel having an upper material input port connected to the lowermaterial output port of the upper inner wall vessel and a lower materialoutput port; a lower outer wall vessel having an upper gas output portand connected to the lower gas input port of the upper outer walledvessel, and surrounding the inner walled vessel such that a gasconveying space is interposed between said inner walled vessel and saidouter walled vessel; and a heater positioned in the lower stage. Thereactor apparatus can include multiple repeating units of theabove-mentioned upper and lower units in a cascading or staircase-typereactor arrangement. The heater can be located in alternative positionsof the reactor, for example, another heater can be added to one or moreof the intermediate repeating units.

BRIEF DESCRIPTION OF THE DRAWING

Example embodiments of the present invention can be understood withreference to the following drawing. The components in the drawings arenot necessarily to scale.

FIG. 1 is a schematic of multistage continuous reactor apparatus,according to an embodiment of the invention.

DETAILED DESCRIPTION

The embodiments of the present invention include processes and systemsfor pyrolysis of hydrocarbonaceous material found in waste, for example,thermoplastic polymers, theremoset polymers, and blends thereof, suchthat they are converted into useful products yielding enhanced amountsof aromatic compounds.

In one embodiment a process for pyrolysing hydrocarbanaceous materialincludes charging a reactor with feed material comprisinghydrocarbonaceous material, heating the feed material, collectingproduct from the reactor which is anaerobic in operation. The term“anaerobic” herein means that, upon initial heating, the reactorcontains less than about 3% by volume oxygen, in an alternativeembodiment, less than about 2% by volume oxygen, in an alternativeembodiment, less than about 1% by volume oxygen, and in yet analternative embodiment, from about 0.01% to about 1% by volume oxygen,based on the internal volume of the reactor. The process results in atleast 5%, in an alternative embodiment, from about 10% to about 90%, inan alternative embodiment from about 15% to about 70%, and in yet analternative embodiment, from about 20% to about 60% of the organiccarbon atoms which are not present in an aromatic ring of a compound ofthe feed material are present in an aromatic ring of a compound in aliquid portion of the product. The term “aromatic ring” is understood bythose of ordinary skill in the art as six carbon atoms bonded in a ring,and carbon atoms that are present in an aromatic ring does not includethe carbon atoms found in pendant chains and functional groups which arebonded to the aromatic ring. That is, the amount of aromatic ringspresent in the product is greater than the amount of aromatic ringspresent in the feed material. The pyrolytic process according to thevarious embodiments described herein, demonstrate that random mixturesof feed material containing hydrocarbonaceous material produce newaromatic rings.

The conversion of the amount of the organic carbon atoms which are notpresent in the aromatic rings of compounds of the feed material to theamount of organic carbon atoms found in aromatic rings of compounds ofthe liquid portion of the product, can depend upon the amount of organiccarbon atoms that are not initially present in aromatic rings of thefeed material. For example, if the feed material contains organic carbonatoms, 80% of which are not present in an aromatic ring of a compound,then the pyrolysis process will convert at least 4% of those carbonatoms into carbon atoms which are present in the rings of aromaticcompounds of the liquid portion of the product. In another example, ifthe feed material contains organic carbon atoms, 35% of which are notpresent in an aromatic ring of a compound, then the process will convertat least 1.75% of those organic carbon atoms into carbon atoms found inthe rings of aromatic compounds found in the liquid product. The amountof organic carbon atoms which are present in aromatic rings of compoundsand those which are not present in aromatic rings of compounds can bemeasured by the Carbon 13 NMR test which is well known to those ofordinary skill in the art. The feed materials, in the variousembodiments described above, contain organic carbon atoms, and at least20%, in some examples, at least 40%, and yet in other examples, at least50% of the organic carbon atoms are not present in aromatic rings of thefeed material. That is, at least half of the organic carbon atomspresent in the feed material are bonded in an arrangement that isdifferent than an aromatic ring bonding arrangement. The feed materialcan include a random mix of scrap that includes at least about 70% byweight, alternatively, at least about 80%, and yet alternatively, atleast about 90% hydrocarbonaceous material, wherein thehydrocarbonaceous material includes at least two distinct compositions.In another embodiment the feed material can also include up to about 25%by weight metal. The metal increases heat conduction throughout thepyrozylate mass which increases the effective heating rate which reducesthe time required to achieve exhaustive pyrolysis.

Hydrocarbonaceous materials can include thermoplastic polymers such as,for example, polyethylene, polypropylene, polyester,acrylonitrile-butadiene-styrene (ABS) copolymers, polyamide,polyurethane, polyethers, polycarbonates, poly(oxides), poly(sulfides),polyarylates, polyetherketones, polyetherimides, polysulfones,polyurethanes, polyvinyl alcohols, and polymers produced bypolymerization of monomers, such as, for example, dienes, olefins,styrenes, acrylates, acrylonitrile, methacrylates, methacrylonitrile,diacids and diols, lactones, diacids and diamines, lactams, vinylhalides, vinyl esters, block copolymers thereof, and alloys thereof.Polymers yielding halogenated material upon pyrolysis, for example,polyvinyl chloride, polytetrafluoroethylene, and other halogenatedpolymers, can be corrosive but can be tolerated.

Hydrocarbonaceous materials can also include thermoset polymers such as,for example, epoxy resins; phenolic resins; melamine resins; alkydresins; vinyl ester resins; unsaturated polyester resins; crosslinkedpolyurethanes; polyisocyanurates; crosslinked elastomers, including butnot limited to, polyisoprene, polybutadiene, styrene-butadiene,styrene-isoprene, ethylene-propylene-diene monomer polymer; and blendsthereof.

Hydrocarbonaceous material found in scrap material can have acombination of thermoplastic and thermoset polymers, for example, tires,paint, adhesive, automotive shredder waste (fluff), etc., and can beused as feed material according to the various embodiments of thepyrolytic process herein. Other hydrocarbonaceous materials which can beutilized are believed to include coal, shale oil and tar sands.Carbohydrates may be present in small amounts; however, they are notpreferred materials as the major portion of the hydrocarbonaceousmaterial. In general, carbon and hydrogen atoms comprise at least 55weight percent of the total hydrocarbonaceous material, in some cases,at least 65 weight percent, and alternatively, at least 70 weightpercent of the total hydrocarbonaceous material present in the feedmaterial and charged to the process.

The amount of feed material charged into the reactor is generally high.For example, in one embodiment the feed material can range from about 25to about 635 Kg/m³ [from about 100 to about 2,500 lb. per 64 foot³], inanother embodiment from about 50 to about 500 Kg/m³ [from about 100 to2,000 lb. per 64 ft³], and in yet an alternative embodiment from about75 to about 375 kg/m³ [from about 300 to 1,500 lb per 64 foot³]. In aprocess in which the feed material is agitated, for example, when thereactor size has a diameter of about 2.44 m [8 foot], the amount of feedmaterial per unit volume of reactor can be higher. The amount of feedmaterial charged into the reactor can range as from about 50 to about750 kg/m³ [200 to about 3,000 lb per 64 ft³], alternatively from about50 kg to about 625 kg [200 to about 2,500 lb per 64 ft³], andalternatively from about 75 to about 500 kg/m³ [from about 300 to about2000 lb per 64 ft³]. Generally the optimum amount of feed materialcharged into the reactor will vary according to the type of chargematerial and agitation, all of which relate to the effective heatingrate of the charge.

The internal volume of the reactor is greater than about 0.0283 cubicmeters [1 cubic foot], in an alternative embodiment the internal volumeranges from about 0.0850 cubic meters [3 cubic feet] to about 84.95cubic meters [3,000 cubic feet], and in yet an alternative embodiment,ranges from about 0.2265 cubic meters [8 cubic feet] to about 56.63cubic meters [2,000 cubic feet]. Should some sort of an internal mixerbe utilized, the internal volume is usually larger as from about 0.0850m³ to about 113.27 m³ [3 cubic feet to about 4,000 cubic feet] and oftenfrom about 0.2832 m³ to about 70.79 m³ [10 to 2500 cubic feet]. Althoughlarger sizes can be utilized, they are generally impractical because offabrication costs, engineering considerations, heat transfer issues, andthe like. Naturally, the rate of agitation and the agitatorconfiguration are parameters that influence optimal reactor design. Ingeneral, gentle agitation will produce a pyrolyzate bed having lowerturbulence which will reduce the chance of entrainment of carbonparticles and/or other bed particulates into the pyrolytic gases andresultant condensate.

Although the reactor shape can vary, a reactor having a high volume tosurface area is desirable, for example, in reactor shapes that arecubical, rectangular and spherical. In another example embodiment thereactor is a spheroid or pipe-like. Due to the high heating rates andtemperature, the reactor is typically made of a material having a highmelting point, for example, steel, stainless steel, or high temperaturealloy, for example, Inconel.

The heating temperature applied to the reactor can range from about 426°C. [800° F.] to about 1,371° C. [2,500° F], in an alternativeembodiment, from about 649° C. [1,200° F.] to about 1,260° C. [2,300°F], an in yet an alternative embodiment from about 815° C. [1,500° F.]to about 1,093° C. [2,000° F]. The heat source can be any conventionalsource yielding the above temperatures and can include, for example,natural gas, electric heat, coke, and the like. The heating rate can beconstant, variable, and intermittent, for example.

It has been found that the use of low input heat rates into largeamounts of feed material, yield products that contain alkylatedaromatics which are desirable feed stocks for many commercialapplications. The heat input rate per unit mass of feed material canrange from about 0.232 mJ/kg/hr [100 BTU/lb/hr] to about 116.2 mJ/kg/hr[50,000 BTU/lb/hr], in another embodiment from about 11.62 mJ/kg/hr[5,000 BTU/lb/hr] or less, in another embodiment, about 4.65 mJ/kg/hr[2,000 BTU/lb/hr] or less, in an alternative embodiment, about 1.16mJ/kg/hr [500 BTU/lb/hr] or less. It has been observed that low heatinput rates along with the formation of a pyrolyzate mass or “pyrozylatebed” yields proportions of products not heretofore achieved. However, iftoo low a heating rate is used the process may not be of economicinterest, because the time to exhaustive pyrolysis is greater thanpractical.

The average area of loading of the feed material on the heated surfaceof the reactor upon initial heating can range from about 9.0 kg/m² toabout 400 kg/m², in an alternative embodiment from about 20 kg/m² toabout 375 kg/m² and in yet another embodiment, from about 30 kg/m² toabout 250 kg/m². The bed depth, or thickness of the feed material alongthe heated surface of the reactor, can be determined by the average arealoading of the feed material within the reactor. The average area ofloading of the feed material takes into account the variations in thebed depth depending upon the reactor geometry.

In the example embodiments described above, the reactor has sufficientdepth to enable formation of a pyrolyzate char layer during pyrolysisand also sufficient head space above the feed material to allow escapeof products in the form of a gaseous stream, at least a portion of whichis condensable into a liquid portion of the product. The internal volumeof the reactor is consumed by the volume of the feed material, theinterstitial volume between particles of the feed material, and headvolume or “head space” above the feed material (Internal Volume ofReactor=Volume of Feed Material+Interstitial Volume+Head Space). A largehead space provides adequate surge volume and reduces the risk ofplugging the movement of product through the system. The “free volume”is defined as the sum of the interstitial volume and the head space(Free Volume=Interstitial Volume+Head Space). The free volume increasesas the pyrolysis process continues to exhaust the feed material toproduce product. Upon initial heating, the interstitial volume normallydecreases due to the melting or the collapse of the feed material uponheating. For example, a charge of feed material containing whole tirescan collapse upon heating thereby greatly increasing the head spacewhile also decreasing the interstitial volume. The reactor has at leastabout 25% free volume upon initial heating, in some embodiments at least40% free volume upon heating, and in alternative embodiment at leastabout 50% free volume upon heating.

The interstitial volume can depend upon the particle size of the feedmaterial. Bulky scrap material used as feed stock, such as scrappedtires and the like, may be shredded to the form of chunks, pellets, orsmall particles. This is of advantage for feeding a continuous reactor.The chunky nature of the material forming a pyrolytic bed can also be ofadvantage in certain situations; e.g., the interstitial volume presentin a charge of such chunks permits thermally conduction within thepyroyzlate charge. Melted thermoplastic portions of the charge and wellas hot escaping vapors may enhance heat transfer to the chunks, eventhough chunks have decreased contact area with the reactors heatedsurfaces. However, in general, reduction of size of particles of feedmaterial smaller than about 5 millimeters has little advantage in theprocess.

An effective heating rate can be defined as follows:

Effective Heating Rate=[(BTU/hr)/lbs]/Time to Exhaustive Pyrolysis

For example, 10001 bs of thermoplastic heated at a given rate takes Xtime to pyrolize. !0001 bs of thermoset in the same reactor using thesame conditions takes much longer than X time to pyrolize. The rangingtest of Example 9 described below demonstrated that, thermallyconductive material, (i.e. metallic wire,) +thermoset material, can bepyrolized in a time close to X. The decreased time to exhaustivepyrolysis is due to the increase of the effective heating rate caused bya good thermal conductor, like bead and/or tread wire.

Time to exhaustive pyrolysis starts with the evolution of pyrolyticproducts and ends with the substancial exhaustion of condensiblepyrolytic products. An end point based on noncondensibles is notpractical. These are relative definitions to some control or standard.While theoretically imperfect this definition and other similardefinitions may still provide a practical working standard ofcomparison.

The pyrolytic process can also be described in terms of an alternativeheat flux. Therefore, in one embodiment the feed material is heated atan initial heat flux per average area loading of feed material of lessthan about 3.0 kW·m²/kg², in an alternative embodiment from about7.0×10⁻⁴kw·m²/K² to about 3.0 kW·m²/kg², in alternative embodiment fromabout 0.001 kW·m²/kg² to about 1.5 kW·m²/kg², and in yet an alternativeembodiment from about 0.005 kW·m²/kg² to about 0.5 kW·m²/kg².

The pyrolytic process described above can be carried out at atmosphericpressure or at a low pressure, for example, less than about 550 kPa[about 80 psig], in alternative embodiment less than about 350 kPa[about 50 psig], and in yet alternative embodiments less than about 100kPa [about 14.7 psig]. The pressure is due to internal generation ofgasses and can vary as the pyrolitic reaction proceeds.

Time to exhaustive pyrolysis starts with the evolution of pyrolyticproducts and ends with the substancial exhaustion of condensiblepyrolytic products. Exhaustive pyrolysis is attained when there is asharp drop in the quantity of liquid product generated, and the vaportemperature usually coincides with a substantial temperature drop intemperature, for example, a temperature drop of at least about 56° C.[100° F.] within a time period of about 10 to 15 minutes, whilemaintaining a constant heat rate. In the example embodiment describedabove, the exhaustive pyrolysis is reached in about eight hours or less,in an alternative embodiment, about three hours or less, in analternative embodiment from about 15 minutes to about two hours, and inan alternative embodiment from about 30 minutes to about 1.5 hours. Theliquid portion of the product collected upon exhaustive pyrolysiscontains at least about 5% greater number of organic carbon atomspresent in aromatic rings compared to the number of organic carbon atomspresent in aromatic rings of the feed material.

In another embodiment of the pyrolytic process, there is no addedcatalyst in the reactor. Residual catalyst, however, may be found in thefeed material, such as for example, in thermoplastic polymers, thermosetpolymers, and blends thereof.

In the various embodiments of the pyrolytic process described above,there is no added carrier gas or diluent gas present in the reactor.Carrier gases, such as, for example, helium, argon, nitrogen, carbondioxide, may be present in the reactor, in the case where the reactorwas purged prior to heating to reduce the amount of oxygen gas to justtrace amounts, for example, less than about 1% oxygen by volume of thereactor. Residual carrier gas present in the reactor will be displacedfrom the reactor by the gaseous product stream that evolves duringpyrolysis process.

In another embodiment the pyrolitic process further includes collectinga gaseous stream which evolves from the reactor and condensing thegaseous stream to obtain a liquid portion of the product. For example,the reactor can include a gas take-off stream that has a condenser, orother appropriate equipment that condenses the gaseous stream to aliquid stream. Additional equipment, for example, heat exchangers,instrumentation, catalytic performers, stripping and distillationcolumns and the like may be part of an integrated downstream processfrom the reactor. For example, the gaseous stream can be condenses bycooling the gaseous stream to about 80° C. or less, in an alternativeembodiment to a temperature of less than about 30° C. or less.Furthermore, compounds generated from the gaseous stream, for examplegases containing from one to four carbon atoms, can also be used as aheat source to fire the reactor.

The pyrolytic process according the embodiments described above can beconducted in a batch reactor or a continuous reactor. When the pyrolysisprocess take place within a continuous reactor such that the feedmaterial is gradually conveyed along a reactor bed, the conveyed bed canbe divided into a plurality of reactor units each treated as a separateentity as it moves along the reactor bed with each separate unit beingwithin the reactor volume size as set forth above. For example, internalreactor volume ranges from about 1.7 cubic meters to about 113.27 cubicmeters.

Ancillary heat transfer methods, such as, preheating, predrying,recirculation, etc, that are not easily obtained or perhaps not possiblein a batch reactor can be utilized in a continuous process. It will beunderstood by one skilled in the art that the heat requirements of acontinuous process will vary from section to section, i.e., more heatmay be applied to the initial section which has the full loading of thefeed material charged as compared to a latter section where a portion ofthe feed material has been pyrolyzed, thereby reducing the average arealoading of feed material on the heated surface of the reactor.Similarly, in a batch reactor, although a constant rate of heat may beused, the heat flux to the charge will increase as pyrolysis occurs andthe average area loading of feed material on the heated surface of thereactor decreases.

The formation of a the pyrolzate/char layer or bed, is due to the highheat applied to a surface of a vessel, essentially breaking down thefeed material and yielding various pyrolysis products. The pyrolyzatebed depth that forms during a particular pyrolysis reaction will varyaccording to parameters such as heat rate, amount of charge utilized,type of material in charge, pressure, agitation, and the like.Generally, a char layer portion of the pyrozylate mass can have athickness that is about 10 cm. [about 4 in.] or less, although it may begreater.

It has been observed that, for a given steady heating rate, the rate ofpyrolysis, that is, the rate at which gaseous products are evolved, isusually not constant. Different rates of pyrolysis and/or types ofproducts from within the pyrolysis vessel can occur. Above the initialactivation temperature for a given pyrolytic system, various plateaus ofproduction rate and product temperature have been observed.

Generally, the present invention tends to produce higher amounts ofunsaturated organic compounds such as cycloalkenes and aromaticcompounds, when compared to conventional pyrolytic processes. The endproducts, in the form of solid, liquid and gas, can be used for commonand conventional applications. For example, the char from the process issuitable for use with coal as a boiler fuel, and a considerable portionof the condensable liquids can be used as petrochemical feedstocks.

FIG. 1 is a schematic illustration of a reactor apparatus for carryingout the pyrolytic process according to an example embodiment of thepresent invention. Feed hopper 10 which feeds polymer scrap to a inclineconveyor 12 which at its upper end feeds the scrap into an auger feed 14from where it is fed into a rotary dryer 16 having a flue gas exit pipe18. An auger/air lock 20 feeds a multi stage double walled vessel showngenerally at 22. The vessel 22 includes an upper inner walled vessel 24and an upper outer walled vessel 26. There is upper vertical connectingtube 28 between the upper inner walled vessel 24 and a lower innerwalled vessel 30. The lower inner walled vessel 30 is surrounded by alower outer walled vessel 32 a lower discharge tube 34 extends from thelower inner walled vessel through the lower outer walled vessel to ahorizontal discharge tube with air lock 36 which discharges char 38. Aline 40 extends from the upper inner walled vessel 24 through the upperouter walled vessel to heat exchanger 42 and then to valve 44 to aliquid line 46 for product storage and a loop gas line 48 which extendsto valve 50 on the lower outer walled vessel 32. Line 52 extends fromthe upper inner walled vessel 24 through the upper outer walled vessel26 to heat exchanger 54. Line 56 extends from lower inner walled vessel30 through lower outer walled vessel 32 to heat exchanger 58 lines 52and 56 extend respectively from heat exchangers 54 and 58 to a valve 60which diverts the stream to liquid line 62 which extends to productstorage. Loop gas line 64 which extends back to valve 50 to inject gasinto burner 51 which leads to the space between the lower outer walledvessel 32 and the lower inner walled vessel 30. This hot-burned flue gascontinues to flow upwardly between the upper inner walled vessel 24 andthe upper outer walled vessel 26 and then past the auger air lock 20 soas to heat the material flowing downwardly through the auger air lock20. The hot flue gas then flows through 16 then out 18, preheating theincoming material.

The present invention will be better understood by reference to thefollowing examples.

EXAMPLES

Description of Reactors and Heat sources:

Reactor I was a 60.96 cm by 5.08 cm diameter [24 in. by 2 in. diameter]SCH 40, 304 stainless steel pipe which was capped at the ends. Thereactor was heated with a propane burner having a flame temperature ofapproximately 982° C. [1,800° F.] with a burner size of approximately60.96 cm long and 5.08 cm wide [24 in. long and 2 in. width]. Thereactor was constructed of two pipe sections connected to a central“tee” which provided a connection for the pyrozylate gases to thecondenser. The reactor contained 0.455 kg [1 lb] of the feed materialand was heated at the rate of 26.42 kW/kg [41,000 BTU per pound perhour].

Reactor II was a 91.44 cm by 10.16 cm diameter [36 in. by 4 in.diameter] SCH 40, 304 stainless steel pipe containing two 150 # flangeson the ends thereof covered by 150 # blind flanges. A 5.08 cm [2 in.]side arm was welded to the center of the 10.16 cm [4 in.] pipe toprovide a connection for pyrozylate gases to the condenser. The reactorcontained 4.545 kg [10 lb] of the feed material which was heated withthe same burner as Reactor I, resulting in a heating rate of 2.642 kW/kg[4,100 BTU per pound of feed material per hour].

Reactor III was a 1514 liter [400 gallon] 304 stainless steel reactorhaving spherical heads with a 1.22 m [4 foot] diameter section of 1.22 m[4 foot] radius sphere and 0.9525 cm [⅜ in.] thickness. The shell of thereactor was 0.635 cm by 1.22 m in length by 1.22 m in diameter [¼ in. by4 foot in length by 4 foot in diameter]. This reactor was heated with apropane heat source of about 117.15 kW [400,000 BTU per hour] at atemperature of approximately 982° C. [1,800° F].

Standard conventional equipment such as a heat exchanger (condenser),surge tank and pressure regulator for escaping gas, were attached to thereactors to extract and collect the products. The internal pressureduring the pyrolysis reactions were low, generally of the range of 0 toabout 35 kPa [0 to about 5 psig].

All reactors were purged three times prior to the pyrolysis bypressurizing to about 100 kPa [15 psig] with CO₂ and then venting toatmospheric pressure.

Pyrolysis of Polyisoprene/Polystyrene Blends

A 50/50 (by weight) blend of cis-polyisoprene (Goodyear Natsyn® rubber),containing 96+% (by weight) of synthetic cis-1,4-polyisoprene, and beadsof polystyrene commercial grade clear were added to the variousreactors.

Summary of Observations from Examples 1-4 Induction Time to Pyrolysisand Duration of Pyrolysis Time, minutes To Initial Feed Material Liq.End of Total EX..# Reactor kg lb Prod'n Pyrolysis¹ Heating 1 I PI/PS0.455 1 13 17 30 2 II PI/PS 4.545 10 30 80 110 3 III PI/PS 45.45 100 2199 120 4 III PI/PS 454.5 1000 27 343 370 ¹End of pyrolysis is defined astime during constant application of heat at which vapor temperaturedrops ~56° C. [100° F.] or more in 10 min., and/or liquid productionslows appreciably.

Example 1

Reactor I was charged with 0.455 kg [1 lb] of the above blend. The totalheating time to exhaustive pyrolysis was 30 minutes.

Example 2

Reactor II was charged with 4.545 kg [10 lb] of the above blend. Thetotal heating time to exhaustive pyrolysis was 1 hour and 55 minutes.

Example 3

Reactor III was charged with 45.455 kg [100 lb] of the above blendresulting in a heating rate of 2.58 kW/kg [4,000 BTU per pound feedmaterial per hour]. The total heating time to exhaustive pyrolysis was 2hours.

Example 4

Reactor III was charged with 454.54 kg [1,000 lb] of the above blendyielding a heating rate of 0.258 kW/kg [400 BTU per pound feed materialper hour]. After approximately 6 hours and 10 minutes exhaustivepyrolysis was reached.

Table I sets forth the compounds found in the liquid products yielded byeach of the Experiments. Experiments 1, 2, 3 and 4 relate as controls toeach other showing how pyrolysis and its products varied as theparameters of size and heat rate were changed. The amount of aromaticsproduced shows a significant increase in applicant's process relative tothat of the prior art. Experiment 3 is believed to show conditions at ornear a peak production of aromatics.

It is apparent from Table I that several unexpected increases ordecreases of various components of the liquid product were obtained aswell as differing amounts of total aromatic compounds which are notsuggested by the prior art. For example, the amount of toluene rangedfrom about 4.1 to about 7.6 percent by weight, the amount of ethylbenzene ranged from about 3.2 to 18.8 percent, the amount of(1-methylethenyl)benzene, [a-methylstyrene], ranged from about 3.8 to7.7 percent, the amount of styrene ranged from about 33.2 to 60.2percent, and the amount of 1-methyl-4-(1-methyl-ethenyl)-cyclohexene[limonene] ranged from about 11.2 to about 21.5 percent.

TABLE I Polyisoprene-Polystyrene Pyrolysis EXPERIMENT 1 2 3 4 CompoundPercent of Pyrozylate by Weight 2-butene 0.2 0.1 0.5 0.53-methyl-1-butene 0.1 0.1 0.1 0.2 2-pentene 0.1 0.2 0.4 0.52-methyl-1,3-butadiene 4.4 3.2 4.2 4.4 (1-methylethenyl) cyclopropane0.1 0.1 0.2 0.2 1-methyl-1,3-cyclopentadiene 0.1 0.1 0.2 0.11,5-dimethylcyclopentene 0.2 0.1 0.2 0.1 2-methyl-1,3-pentadiene 0.2 0.20.5 0.4 3-methyl-1,3,5-hexatriene 0.2 0.2 0.3 0.23-methyl-2,4,-hexadiene 0.5 0.5 0.4 0.6 2,4,4-trimethyl-2-pentene 0.10.1 0.1 0.1 Toluene 4.1 5.1 5.6 7.6 1,2-dimethylcyclohexane 0.2 0.2 0.10.2 2,3-dimethyl-1,4-hexadiene 0.2 0.2 0.3 0.3 C₈H₁₂ unsaturatedaromatic 0.1 0.1 0.1 0.1 Ethyl Benzene 3.2 6.3 3.2 18.8 C₉H₁₄unsaturated aromatic 0.5 0.1 0.2 0.1 (1-methylethyl) benzene 0.3 0.7 0.64.9 C₁₀H₁₆ unsaturated aromatic 0.2 0.2 0.1 0.1 Styrene 54.6 51.0 60.233.2 1,2-dimethyl benzene 0.3 0.3 0.9 0.2 C₁₀H₁₆ unsaturated aromatic0.3 0.3 0.2 0.2 Propyl Benzene 0.4 0.6 0.7 0.4 (1-methlyethenyl) benzene4.3 7.1 3.8 7.7 1-methyl-5-(1-methylethenyl)- 4.0 0.3 0.5 0.4cyclohexene 4-methyl-1-(1-methylethenyl)- 0.5 0.2 0.1 0.1 cyclohexene1-methly-4-(1-methylethenyl)- 21.5 19.0 11.2 14.1 cyclohexene3,7,7-trimethylbicyclo 0.3 0.4 0.1 0.6 [4.1.0] -hept-2-ene1-methyl-4-(1-methylethyl)- 0.7 0.6 0.7 0.5 cyclohexene2,3,6-trimethyl-1,5-heptadiene 0.3 0.3 0.4 0.5 1-ethyl-2-methyl-benzene0.5 0.7 1.2 0.8 1-ethyl-3-methyl-benzene 0.1 0.1 0.4 0.12-ethyl-1,3-dimethyl-benzene 0.3 0.3 0.3 0.2 1-pentenyl-benzene 0.5 0.30.7 0.6 1,2,3-trimethyl-benzene 0.1 0.1 0.2 0.1

It was unexpected that significant amounts of(1-methylethenyl)-cyclopropane, 1-methyl-1,3-cyclopentadiene,1,5-dimethylcyclopentene, 2-methyl-1,3-pentadiene,1,2-dimethylcyclohexane, and, most unusually,3,7,7-trimethyl-bicyclo-[4.1.0]-hept-2-ene were produced. Also presentwere 3-methyl-2,4-hexadiene, 2,3-dimethyl-1,4-hexadiene,2,3,6-trimethyl-1,5-heptadiene and 3-methyl-1,3,5-hexatriene (acumlene); all were present in all samples. These dienes and trienes arethe apparent precursors of many of the aromatic(s).

As a whole, large reductions or increases occurred in various compoundsas compared to previous pyrolytic methods. In particular, the recoveryof a high percentage of the feed material as aromatic compounds in theliquid product differs from the prior art.

The data shown in Table III-A was obtained in the following ways:pyrosylate liquid and char are reported as weight of recovered materialdivided by feed material weight. Gas, as stated, is a mass/materialbalance calculated by difference.

TABLE III-A Polyisoprene-Polystyrene Pyrolysis EXAMPLE 1 2 3 4 FeedMaterial wt., 0.454 4.545 45.45 454.5 kg [lb] [1] [10] [100] [1000]Pyrosylate Liquid 91%  95.8%  92.0%  94.625%  by direct wt. Char bydirect wt. 1% 1.1% 1.7% 3.700% Gas by difference 8% 3.1% 6.3% 1.675%

One can compare the recovery of Styrene in Examples 1-4 with the styrenepresent in the feed material. If all of the polystyrene in the feedmaterial reverted to styrene in the liquid product recovered from thepyrolysis, then the weight of recovered styrene should equal the weightof polystyrene charged in the feed material. This calculation isillustrated below with respect to Example 1.

Wt. % liquid product=91% (see Table III-A)

Wt. % Styrene in liquid product=54.6% (See Table I)

Wt. % Styrene recovered=91%×54.6%=49.686%

Wt % Styrene expected from polystyrene in feed material=50%

Data for Examples 1-4 are given below in Table IV

TABLE IV Styrene Output Polyisoprene-Polystyrene Pyrolysis Styrenetreated as a separate species EXAMPLE 1 2 3 4 Polystyrene in Reactor0.227 kg 2.273 kg 22.727 kg 227.27 kg Feed material, kg [lb] [0.5 lb][5.0 lb] [50.0 lb] [500.0 lb] Styrene in Product,   49.686%   48.858%55.384% 31.455% Wt. % Difference from −0.3140% −1.1420% 5.3840% −18.55%Complete Stryene Recovery, Wt. %

Example 3 shows more styrene out than in, demonstrating conversion ofisoprene. This teaches away from known art.

The increase of aromatics from these experiments can be calculated bysumming the weight of the aromatic compounds detected in the recoveredliquid product, multiplying by the weight percent liquid recovered anddividing by the know weight of the aromatic portion of the feedmaterial, i.e., polystyrene. For illustration, the calculation forExperiment 1 is shown below:

Initial Feed Material=0.454 kg [1 lb]

Liquid product, wt. % of initial Feed Material=91%

0.454 kg×0.91=0.413 kg [0.91 lb]

Weight % Aromatics in Liquid Product (sum of yields from Table I)=69.7%

Weight Aromatics in Liquid Product

0.413 kg×0.697=0.288 kg [0.6344 lb]

Increase In Aromatics=Weight Aromatics in Liquid Product−Weight ofAromatic in feed material (i.e. polystyrene)

0.288 kg−0.227 kg=0.061 kg [0.13427 lb]

% Increase in Aromatics=Weight increase/Weight of Initial

0.061 kg/0.227 kg=13.4%

Results of this analysis for Examples 1-4 are given in Table V below.

When the total aromatic content of the liquid product is considered,Examples 1-4 all indicated greater weight percent aromatic materials inthe liquid product than in the polystyrene of the feed material. Thebalance of the liquid product consisted of non-aromatic compounds.

TABLE V Total Output from Polyisoprene-Polystyrene Pyrolysis WeightPercent Aromatics in Liquid Product EXAMPLE 1 2 3 4 Aromatics inPyrosylate 69.7% 73.1% 78.3% 74.8% (from Table I) Total AromaticsRecovered, 63.4% 70.0% 72.0% 70.8% Wt. % Wt. % Aromatics Created 13.4%20.0% 22.04%  20.78% 

A further method of demonstrating the invention is to consider only thecreation of aromatic rings from non-aromatic carbons in the feedmaterial. This distinguishes the invention from prior art which mayincrease the weight percent of aromatic compounds in the pyrozylateproduct by alkylation of the aromatic rings present in the feedmaterial. An illustration of a method to perform this accounting isgiven below for Toluene recovered in Example 1.

Wt. Liquid Product=0.455 kg×0.91=0.4136 kg [0.91 lb]

Wt. % Toluene in Liquid Product=4.31%

Wt. Toluene in Liquid Product=0.413 kg×0.0431=0.01696 kg [0.03731 lb]

Kg Mole of recovered Toluene=Wt. Toluene/Mol. Wt. Toluene=0.01696 kg/92g/mol=1.843×10⁻⁴ kg mol [4.055×10⁻⁴ lb mol]

Benzene molar equivalent of toluene in liquid product=1.843×10⁻⁴ kgmol×Mol wt Benzene=1.843×10⁻⁴ kg mol×78=0.01438 kg [0.0316324 lb]benzene molar equivalent

Sample Calculations for Toluene molecular weight 92Polyisoprene/polystyrene Pyrolysis EXAMPLE 1 2 3 4 Total Feed Material,0.455  4.545. 45.455 454.55 kg [lb] [1 lb] [10 lb] [100 lb] [1000 lb]A - Wt. Liquid, 0.413 4.345 41.818 431.12 kg [lb] [0.91] [9.58]  [92.0][946.25] B - Toluene % 4.1 5.1  5.6 7.6 (From Table I) E - Benzene Molar0.01438  0.1883 1.985 27.71 Equivalent wt., [0.0316324]  [0.41423][4.3648] [60.9714] kg [lb]

Similar calculations were carried out for each aromatic species (seeTable II) and the sum result is reported as the Benzene MolarEquivalent. Alternatively, the sum of all E is the Benzene MolarEquivalent. An expectation Benzene Molar Equivalent value can becalculated for Example 1 which contains 0.2272 kg of polystyrene:

0.2272 kg polystyrene/104 g/mol=2.185×10⁻³ kmol styrene

[4.808×10⁻³ lb mol styrene]

2.185×10⁻³ kmol styrene×78 g/mol Benzene=0.1704 kg [0.375 lb]

Benzene Molar Equivalent

The Increase of Aromatic Rings Bz.Eq. is simply the percent increasebetween the expectation value and the actual test value; e.g., inExample 1:

100%×(0.47202÷0.375−1)=25.872% increase.

TABLE VI Benzene Equivalency Chart EXAMPLE 1 2 3 4 Styrene input, kg0.227 kg 2.273 kg 22.727 kg 227.27 kg [lb] [0.5 lb] [5.0 lb] [50.0 lb][500.0 lb] Benzene Molar 0.1704 1.704 17.04  170.4  Equivalent expect.[.375] [3.75] [37.50] [375.0] Value, kg [lb] Benzene Molar 0.2146 2.43224.404 237.639 Equivalent test [0.47202] [5.3512] [53.6888] [522.8058]value, kg [lb] Increase of Aromatic 25.872% 42.699% 43.170% 39.415%Rings Bz. Eq. by wt. %

The increase in the weight of aromatic species is not due, in general,to the alkylation of existing aromatic rings, but rather to an increasein the number of aromatic rings. SomeAlkylation/Rearrangement/Disruption of the preexisting aromatic ringssurely occurs; however, it is undeniable that a gross feature of theinvention is that new aromatic rings are forming using isoprene as astarting material. The percent increase of aromatic rings issubstantial, up to 43% by weight, which definitely exceeds the valuesreported in the known art. It is the large increase in the number ofaromatic rings, not the alkylation of existing rings, that teaches veryfar indeed, away from the known art.

Pyrolysis of Scrap Tires

Various amounts of scrap tires as set forth in Table VIII were added tothe various reactors. The reactor size, heating temperatures, input rateof heat, initial purge with CO₂ and the like are the same as set forthabove with regard to Reactors I-III. Reactors in Examples 5-8 werecharged with shredded tires which did not contain either bead fabricwire. Reactor III in Example 9 was charged with whole scrap tires. Thefill port of the reactor limited the tires to those of less than 14 inchrim size. Experimental observations are summarized in Table VIII.

TABLE VIII Summary of Data from Examples 5-9 Induction Time to Pyrolysisand Duration of Pyrolysis Time, minutes To Initial Re- Feed materialLiq. End of Total EX. # actor kg lb Prod'n Pyrolysis¹ Heating 5 I Tire0.455 1 12  14  26 Chip² 6 II Tire 4.545 10 38  67 105 Chip² 7 III Tire45.455 100 35 115 150 Chip² 8 III Tire 454.5 1000 80 >>520⁴   >>600⁴  Chip² 9 III Tire, 136.4 300 NM NM ~150-200 Whole³ NM = Not Measured ¹Endof pyrolysis is defined as time at which vapor temperature drops ~100deg F. in 10 min., and/or liquid production slows appreciably. ²Shreddedtires without either bead or belt wire. Average size ~2 cm. ³Whole 13and 14 inch tires with intact bead and belt wire. ⁴Pyrolysis was nottaken to End of Pyrolysis due to excessive time of experiment

Example 9 was performed as ranging test prior to running Examples 8 toestimate the quantity of propane which would be required for the 454.5kg test. Reactor III was charged with 136.36 kg [3001 bs] of wholetires, which included bead and belt wire, was pyrolized. The heatingrate was 0.86 kW/kg [1333 BTU/lb·hr]. The test proceeded with unexpectedspeed, approximately 2 hours. No data was collected on time to firstliquid product, time to end of pyrolysis or composition of liquid.

Later, the 454.5 kg [1000 lb] test on tires was run, using the wire freeshredded tire feed material. Exhaustive pyrolysis could not be reachedin a reasonable time i.e. greater than 10 hrs. The test ended due tofuel depletion, even though 5 to 10 cc/min of liquid product was beingproduced. The recovered pyrozylate mass, 324.77 kg [714.5 lbs], was inan onion like layered condition consisting of an outer carbonized shellof 103.64 kg [228 lbs], an intermediate fused, asphalt-like layer of58.41 kg [128.5 lbs], and an inner core of 143.18 kg [315 lbs], that hadbeen encapsulated by the asphalt layer. The maximum temperatureexperienced in the core was so moderate that the tire cord did notunworst (untwist). The failure to conduct heat into the core of the454.5 kg [1000 lbs] of shredded tire feed material, which was free ofbead or belt wire, and was unexpected as was the complete encapsulationof the mass's center.

TABLE II Tire Pyrolysis EXAMPLE 5 6 7 Compound Percent of Pyrozylate byWeight Ethyl benzene 5.9 10.0 10.0 Benzonitrile 1.4 2.8 2.0(1-methylethenyl) benzene 2.5 1.0 2.9 Styrene 10.1 5.1 6.3 Xylenes 1.62.0 4.3 Propyl benzene 1.2 1.6 1.4 Ethylmethyl benzene 2.0 3.7 4.2Trimethyl benzene 1.9 2.1 3.4 2-ethyl-1,3-dimethyl benzene 0.9 1.5 1.3Benzene 5.9 6.5 6.7 Toluene 11.1 14.3 13.5 4-Methyl-1-Pentene 0.8 0 01-Butene 1.9 0.3 0.3 3-Methyl-1-Butene 0.8 0 0 2-Pentene 1.1 0.6 0.7Cyclopentene 0.4 0.4 0.5 3-Methyl-1,3-Butadiene 3.8 1.8 1.6 3,3 DimethylCyclobutene 0.9 0.9 1.0 1,3-Butadiene 0.4 0 0 Cyclohexene 1.1 0 04-Methyl Cyclopentene 1.3 1.2 1.6 3-Methyl-2,4-Hexadiene 0.6 1.2 1.11,3,5-Hexatriene 0 0.3 0.4 1,4-Cyclohexadiene 0.4 0 01,2-Dimethylcyclohexane 0.5 0.5 0.5 3,3-Dimethyl-1-Butene 1.1 0 1.22,4-Hexadiene-1-OL 0.7 0.8 0.8 5-Methyl-1,4-Hexadiene 1.2 1.3 1.13-Pentene-2-one 1.1 0 0 3,4,4-Trimethyl-2-Pentene 0 1.0 1.2 Formic AcidHeptylester 1.4 0 0 Heptane 0.6 0.9 0.8 2-Methyl-1,4-Hexadiene 1.5 0 02-Chloro-2-Methyl Propane 1.1 1.0 1.2 4-Ethenylcyclohexene 3.0 2.6 2.6Ethenylcyclohexene 0.6 0.6 0.5 1-Chlorohexane 0.5 0 0 2-Octene 0 0 0.41-Octene 0.5 0 0 1-Methyl-4-(1-Methylethenyl) 15.9 15.0 7.7 Cyclohexene1-Butyl-2-Ethylcyclopropane 0.6 0.9 0.5 1,7,7-Trimethylbicyclo[2.2.1]-3.3 4.2 0 Hept-2-ene 2,3,6-Trimethyl-1,5-Heptadiene 1.2 1.7 1.31,2,3-Trimethylcyclopropane 0.7 0 0 3-Chloro-1-Propynl-Cyclohexane 0.4 00 2,2,4-Trimethyl-3-Pentene-1-ol 0.9 1.1 0 2-Dimethylcyclohexene 1.1 1.41.3 2,4,4-Trimethyl-1-Pentene 0.6 0.5 0.3

As indicated by Table II, the pyrolysis of scrap rubbers yielded asignificant amount of aromatic compounds. Inasmuch as scrapped tiresconstitute a major waste product of the United States, the presentinvention has great potential in reducing the stock piling of such tiresand turning them into a useful resource.

Since the exact composition of the tire feed material was not know,i.e., the aromatic vs. non-aromatic ratio of the feed material was notknow, the production of aromatic materials by the process of theinvention was compared with a well know prior art example. U.S. Bureauof Mines investigation #7302 reports tire pyrolysis yields averaging128.3 liters [33.9 gallons] of aromatics per ton (see page 10, HeavyOils). Assume a density of 0.9 for the aromatic oil, a generous figure.Then, 0.9 times 8 lb/gal equals 7.2 lb/gal times 33.9 gal/ton equals244.08 lb/ton aromatics. 244.08 divided by 2000 equals 12.2%, averagearomatic yield by weight.

Calculations similar to those discussed above (see Table V) wereperformed for the values measured for Examples 5, 6 and 7 (See TableIII-B). A comparison of these results showing the total yield ofaromatic compounds are reported in Table III-C along with the valuecalculated above for the Bureau of Mines study. Yields for the Examplesof this invention are approximately double that achieved in the Bureauof Mines study.

TABLE III-B Tire Pyrolysis EXAMPLE 5 6 7 8 Feed Material, kg 0.454 4.54545.45 454.5 [lb] [1] [10] [100] [1000] Pyrosylate Liquid 46% 38.6% 41.5%NA by direct wt. Char by direct wt. 38% 50.6% 44.5% NA Gas by difference16% 10.8% 14.0% NA Aromatics in Pyrosylate 43.0%   52.5% 56.0% NA (TableII)

TABLE III-C EXAMPLE US Bureau 5 6 7 Of Mines % Aromatics by wt. 19.78%20.27% 23.24% 12.2%

It will be appreciated that a process for pyrolyzing hydrocarbons andparticularly plastic or rubber scrap has been described in which thereare an increased amount of aromatics in the output material as comparedto the input materials. It should also be appreciated that the processhas been described for pyrolyzing polymer feed stock which a largevariety of polymers including rubbers, such as automobile fluff andtires and plastics including computer casings, diskettes and circuitboards as well as paints, inks, adhesives and limited amounts of polyvinyl chloride may be included in the feed stock. Accordingly a robustprocess is availed so that expensive feed stock handling and pre sortingoperations may be eliminated or minimized.

While the present invention has been described in connection with thepreferred embodiments of the various figure, it is to be understood thatother similar embodiments may be used or modifications and additions maybe made to the described embodiment for performing the same function ofthe present invention without deviating therefrom. Therefore, thepresent invention should not be limited to any single embodiment, butrather construed in breadth and scope in accordance with the recitationof the appended

TABLE VII Heating/Firing Rate Data For Polystyrene-Polyisoprene andTires EXAMPLE 1, 5 2, 4 3, 5 9 6, 8 A Firing Rate, kW 12.01 12.01 117.15117.15 117.15 BTU/hr 41,000 41,000 400,000 400,000 400,000 B PolymerFeed Material, kg 0.455 4.545 45.455 136.364 454.545 lb 1 10 100 3001000 C Reactor Weight, kg 4.55 45.45 681.80 681.80 681.80 lb 10 100 15001500 1500 D kW/kg_(load) 26.42 2.64 2.58 0.86 0.26 BTU/lb_(load) · hr41000 4100 4000 1333 400 E kW/kg_(total) 2.399 0.240 0.161 0.143 0.103BTU/lb_(total) · hr 3727 373 250 222 160 F Heated Area, m² 0.05 0.151.21 1.21 1.21 ft² 0.52 1.57 13.00 13.00 13.00 G Polymer Load, kg/m²9.34 31.15 37.64 112.91 375.66 lb/ft² 1.91 6.37 7.69 23.08 76.92 H kW ·m²/kg² 2.82709 0.08481 0.06848 0.00761 0.00069 (BTU/lb_(load) ·hr)/(lb_(load)/ft²) 21467.55 644.03 520.00 57.78 5.20 I(kW/kg_(total))/(kg_(load)/m²) 0.25678 0.00771 0.00428 0.00127 0.00027(BTU/lb_(total) · hr)/(lb_(load)/ft²) 1951.595 58.548 32.500 9.630 2.080J Heat Flux kW/m² 246.85 82.28 97.00 97.00 96.82 BTU/ft2 · hr 7830426101 30769 30769 30769 D = A/B E = A/(B + C) G = B/F H = D/G I = E/G J= D · G

1. A process for pyrolyzing hydrocarbonaceous material, the processcomprising the steps of: charging a reactor having a volume of at least1.7 cubic meters with feed material, the feed material comprisingcarbonaceous material; heating the feed material at an initial heat fluxrate that ranges from about 7×10⁻⁴ kW·m²/kg² to about 3.0 kW·m²/kg;collecting liquid product from the reactor; and wherein the reactor issubstantially anaerobic in operation.
 2. The pyrolytic process of claim1, wherein at least about 5% of the organic carbon atoms which are notpresent in an aromatic ring of a compound of the feed material arepresent in an aromatic ring of a compound in a liquid portion of theproduct.
 3. The pyrolytic process of claim 1, wherein at least about 40%of the organic carbon atoms of the feed material are carbon atoms notpresent in aromatic rings.
 4. The pyrolytic process of claim 1, whereinthe feed material is heated at a heat input rate that ranges from about0.25 kW/kg to about 27 kW/kg.
 5. The pyrolytic process of claim 1,wherein the heat rate to the reactor ranges from about 0.3 kW/kg toabout 25 kW/kg.
 6. The pyrolytic process of claim 1, wherein the averagearea loading of the feed material on the heated surface of the reactorupon initial heating, ranges from about 9.0 kg/m² to about 400 kg/m². 7.The pyrolytic process of claim 1, wherein the average area loading ofthe feed material in the reactor upon initial heating ranges from about20 kg/m² to about 300 kg/m².
 8. The pyrolytic process of claim 1,wherein the reactor has at least about 25% free volume upon initialheating.
 9. The pyrolytic process of claim 1, wherein there is no addedcatalyst in the reactor.
 10. The pyrolytic process of claim 1, whereinthere is no added carrier gas present in the reactor.
 11. The pyrolyticprocess of claim 1, wherein the time period for heating is about threehours or less.
 12. The pyrolytic process of claim 1, wherein thehydrocarbonaceous material comprises compounds selected from the groupof: thermoplastic polymers, thermoset polymers and blends thereof. 13.The pyrolytic process of claim 1, wherein the feed material comprises atleast about 70% by weight hydrocarbonaceous material.
 14. The pyrolyticprocess of claim 1, wherein the feed material comprises up to about 25%by weight metal.
 15. The pyrolytic process of claim 1, furthercomprising the step of agitating the feed material during heating. 16.The pyrolytic process of claim 1, wherein the pyrolytic process iscontinuous.
 17. The pyrolytic process of claim 16, wherein the reactorcomprises a plurality of reactor units, each of the plurality of reactorunits having an internal volume that ranges from about about 1.7 cubicmeters to about 114 cubic meters.
 18. The pyrolytic process of claim 17,wherein a reactor unit of the plurality of reactor units contains thefeed material and has at least about 40% free volume upon initialheating.
 19. The pyrolytic process of claim 1, wherein the feed materialhas an average particle size of about 15 centimeters or less.
 20. Thepyrolytic process of claim 1, wherein the feed material comprises, byweight, from about 5% to about 95% thermoset polymer and from about 95%to about 5% thermoplastic polymer.
 21. The pyrolytic process of claim 1,wherein the internal pressure of the reactor is less than about 550 kPa.